Process for combining hydrocarbon gases with hydrocarbon liquids



Patented Jan. 4, 1938 UNITED I STATES PATENT OFFICE PROCESS FOR, COMBINING HYDROCARBON GASES WITH HYDROCARBON LIQUIDS Application September 14, 1934, Serial No. 744,073

Claims.

My new invention relates to chemically com-.

bining hydrogen, hydrogen gases, and hydrocarbon liquids. 1

An object of my new process is to provide a method by which hydrocarbon gasesmay be chemically combined with hydrocarbon liquids to form gasoline. Another object is to provide a method by which hydrogen may be combined with the heavier fractions of petroleum to enhance the value of these fractions for use as lubricants. Other objects of my new invention will be made apparent in the following specification.

My co-pending application Serial No. 12,681 discloses the use of molten sodium as a polymerization catalyst.

My new process will be fully understood from the following description taken in connection with the accompanying drawing. The drawing illustrates diagrammatically in side elevation a form of apparatus by which my new process may be carried out. v

Referring to the drawing, the numeral l designates a furnace which is heated by a fuel burner 2. A tube 3 in which is mounted a pump 5 and a valve 6 leads from pump 5 through furnace land into a tank 8. The extremity of tube 3 which projects into tank 8 is perforated. A pipe 9 in which is mounted a valve In and which is in communication with supplies of both hydrogen and hydrocarbon gas leads to pump 5. A tubenllin which is mounted a pump 12 leads from tank 8 through furnace I and back into tank 8. A pipe l3 in which is mounted a pump I4 and which is in communication with a supply of hydrocarbon liquid leads into tube H at a point intermediate between pump l2 and furnace l. A pipe IS in which is mounted a pump l6 and which is in communication with a supply of molten, metallic sodium is connected into tank 8. A pipe I! in which is mounted a valve 1 and a pump l8 leads from tank 8 into tube 3 at a point intermediate pump 5 and. furnace l. A drain pipe IS in which is mounted a valve 20 leads from the bottom of tank 8. A pipe 2i in which is mounted a pump 22 and a valve 23 leads from the bottom of tank 8 into tube 3 at a point intermediate pump 5 and furnace I. A pipe 22 in which is mounted a valve 25 leads from a point in pipe 2| intermediate valve 23 and pump 22 and thence into tube 3 at a point intermediate furnace l and tank 8. A pipe 26 leads from the top of tank 8 into the lower section of a bubbling type fractionating column 21. A pipe 28 in which is mounted a gas compressor 29 and a valve 38 leads from the top of fractionating column 21 into tube 3 at a point intermediate pump 5 and furnace l. A pipe 30 in which is mounted a valve 3| and a pump 32 and which is in communication with a supply of cold hydrocarbon liquid leads into fractionating column 21 above bubble trays 33. A pipe 34 in which is mounted a valve 35 leads from the bottom of fractionating column 21. A vent pipe 36 in which is mounted a valve 3'l leads from pipe 28. A pipe 39 in which is mounted a valve 40 leads from a point in pipe 28 intermediate valve 38 and compressor 29 through hydrogen activator 4! into tube 3 at a point adjacent tank 8. Hydrogen activator 4i may be of any conventional type such as means for passing hydrogen througha corona or through molten sodium or otherwise. activated hydrogen (H3) is very unstable, the length of pipe through which this activated hydrogen will pass from activator 4i into tank 8 will be of such a length and size that only a small fraction of a second will elapse while hydrogen is flowing from activator 4| into tank 8. A pipe 42 in which is mounted a valve 43 is connected into pipe H at a point intermediate valve l and pump l8 and leads away from the apparatus.

This apparatus will be utilized to carry out my new process in the following manner:

Molten sodium will be delivered into tank 8 in.

sufficient quantity to submerge the perforated extension of tube 3 into tank 8. Heavy hydrocarbon liquid such as fuel oil or heavy distillate which has been obtained from crude oil will be continuously supplied through pipe l3 and pump I l and thence through tube l I and furnace I to the tank 8 in sufficient quantity to partially fill tank 8 and submerge the outlets from tank 8 into pipe i1 and tube H. Hydrocarbon liquid will be withdrawn from the tank 8 through pipe I! by means of pump l8 and discharged from the process to storage tanks through the pipe 42 and valve 43. Hydrocarbon liquid will be withdrawn from the tank 8 by means of pump I2 and will be delivered through tube II and furnace I back into tank 8,

- and this liquid so circulated through tube II will be heated in passage through furnace l to any desired temperature, thus maintaining the tem-.

perature of the oil contained in tank 8 at any desired point. Hydrocarbon gases or hydrogen or .a mixture of these gases will be delivered through pipe 8 to pump 5 and will be forced by pump 5 through tube 3 and through furnace I wherein such gases will be heated to any desired temperature and these'heated gases will then be delivered through the perforations in the extension of As the tube 8 in tank 8. Any gas thus delivered through tube 3 into tank 8 will rise through the bath of molten sodium contained in tank 8 and thence through the body of oil contained in tank 8 and will flow thence through pipe 28, fractionating column 2?, and will be caused to flow by gas compressor 28 from the top of fractionating column 2! through pipe 28 into tube 8 and thence through tube 3 back into tank 8. Relatively cool hydrocarbon liquid will be deliveredthrough pipe 3t] into the upper part of fractionating column 2? and will flow thence downward over bubble trays 33, contacting thereon the gases which will flow upward through fractionating column 2i, and this contact will result in scrubbing from these gases any liquid which may be evaporated in them, and the liquid thus flowed downward through fractionating column 27 will gather at the bottom of this fractionating column and will be delivered thence through pipe 36 and valve 35 to be cooled and re-used or into storage tanks. A part of the liquid thus delivered through pipe 3 1 may be delivered directly into tank 8 through pipe 13 by means of connecting pipe 344 into pipe i The quantity of oil held in tank iiwill be maintained constant by means of continuously withdrawing some of this material through pipe ii, pump 68, pipe 42, and valve 43. The process will be carried out under super-atmospheric pressure. This pressure may be regulated by means of a back pressure valve 3'! mounted in a gas vent pipe 36 which is connected into pipe 28 intermediate fractionating column 2'! and gas compressor 28 and leads from the process. Any excess gas which may accumulate within the apparatus may be vented from the process through pipe 36 and valve 37 As a result of carrying out the above described operations, hydrogen, which has been heated in tube 3 and activated by bubbling through molten sodium, may be contacted with the oil held in tank 8, and, being in an activated state, will thereupon combine with this coil. This combin-,

ing hydrogen with the heavy fractions of petroleum will enhance their value as lubricants. The

' rate at which oil is fed by pump l4 into and through tank 8 will regulate the degree to which such material is treated in passage through tank 8, the treated material being withdrawn from tank 8 as described by pump [8 and delivered from the apparatus through pipe 42.

Several alternate methods of operation which may be found useful are shown. Molten sodium may be withdrawn from the bottom of tank 8 and delivered by means of pump 22 through pipe 2| and thence through heating tube 3 in close contact with the hydrogen or gas flowing through tube 3. Valve 23 may be closed and valve 25 opened and molten sodium may then be delivered by pump 22 from tank 8 through pipes 20 and- 24 into tube 3 and thence into tank 8 accompanying other materials delivered through tube 3 into tank 8. Valve 38 may be closed and valve 40 may be opened and the gas delivered from the top of fractionating column 21 may then be caused to flow through pipe 28, compressor 29, pipe 39 and hydrogen activator 4| and thence into tube 3, and therethrough into tank 8. Hydrogen or hydrocarbon gases may be delivered from an extraneous source directly through pipe 44 and valve 45 into and through activator 4| into the tube 3 and thence into tank 8. Hydrocarbon liquid may be withdrawn from tank 8 by means of pump l8 and may thereby be delivered through pipe I into arouses tube 3 and thence through furnace i in contact with the gas delivered through tube Hydrogen or hydrocarbon gases such as those produced by cracking hydrocarbon materials or uncracked natural gas may be delivered through tube 3 and through tank 8 and may be combined therein with the comparatively heavier hydrocarbon liquid in tank 8 to form gasoline or heavier hydrocarbon liquids.

My new process contemplates maintaining a body of hydrocarbon liquid in a heated condition and bubbling activated hydrogen or hydrocarbon gases through this hydrocarbon liquid, thus effecting a chemical combination between the gases and the liquid. As these gases remain activated for only a short time after contact with molten sodium, I have arranged to bring the molten sodium and gas and hydrocarbon liquid into close contact with each other in order that the gases, after being activated by contact with the sodium, may immediately contact the hydrocarbon liquid with which it is to be united.

As a specific example of one mode of operation of applicants process, hydrocarbon gases such as those obtained from cracking operations may be heated to a temperature in the neighborhood of 500 F. and while under a pressure of 200 pounds per square inch are contacted with molten sodium and then immediately contacted with fuel oil also at a temperature or approxi-- mately 500 F. and under a pressure of 200 pounds per square inch, to produce lighter hydrocarbons, a portion of which boils within the gasoline range.

While the above are conditions under which my process may be carried out, higher and lower temperatures and pressures may be employed, depending upon the charging stock and product desired. In general temperatures within the range of 210 F. and 800 F. and pressures approximating 50 pounds per square inch to 250 pounds per square inch will suilice. Since the hydrocarbon gases remain activated for only a short period of time, the contact time \will of necessity be very short.

While I have described in detail a method by which my new process may be carried out, it should be understood that I do not propose to limit myself to these details but expect to broadly claim all of the advantages inherent in my new process.

I claim:

1. The process of combining hydrocarbon liquids with hydrocarbon gases which comprises circulating an endless stream of hydrocarbon liquid, circulating an endless stream of hydrocarbon gas, contacting the two streams at one point and activating the stream of hydrocarbon gas with a catalyst comprising molten sodium in the immediate vicinity of said point to effect combination between said hydrocarbon liquid and said hydrocarbon gas.

2. The process of combining relatively heavy hydrocarbon liquids with hydrocarbon gases which comprises circulating an endless stream of hydrocarbon liquid, contacting said stream with an endless circulating stream of activated hydrocarbon gas to thereby effect combination between said hydrocarbon liquid and said hydro carbon gas and maintaining said hydrocarbon gas in an activated state at the point of contact of the two streams by effecting said contacting in the presence of a body of molten sodium.

3. The process of combining hydrocarbon liqquids with hydrocarbon gases which comprises circulating an endless stream of hydrocarbon liquid, contacting said stream at one point with an endless circulating stream of hydrocarbon gas, activating said stream of hydrocarbon gas by passing the same through a body of molten sodium at substantially the point of contact of the two streams to thereby effect combination between said hydrocarbon liquid and said hydrocarbon gas and withdrawing liquid products from said stream of hydrocarbon liquid after said contacting.

4. The process of combining hydrocarbon liq uids with hydrocarbon gases which comprises circulating an endless stream of hydrocarbon liquid, contacting said stream at one point with an endless circulating stream of hydrocarbon gas,.

activating said stream of hydrocarbon gas substantially at the pdint of contact of the two streams by effecting said contact in the presence of a body of molten sodium and causing said gas to flow upwardly through said sodium to thereby effect combination between said hydrocarbon liquid and said hydrocarbon gas and withdrawing liquid products from said stream of hydrocarbon liquid after said contacting.

5. The process of combining hydrocarbon liquids with hydrocarbon gases which comprises, heating a stream of hydrocarbon gases, heating a stream of hydrocarbon liquids, activating said stream of hydrocarbon gases by bubbling through a mass of molten sodium, contacting said activated hydrocarbon gases and said hydrocarbon liquid in the immediate vicinity of said sodium mass, and heating a portion of said molten sodium by introducing the same into the hydrocarbon gas stream prior to said heating step.

MALCOLM: P. YOUKER. 

